Imidohalides and process of preparing them and their hydrolysis products



Patented Oct. 2, 1951 IltflDOHALIDES AND PROCESS OF PREPAR- ING THEM AND THEIR HYDROLYSIS PRODUCTS Paul L. Barrick, Boulder, Colo., assignorto E. I. du Pont de Ncmours & Company, Wilmington, Del., a corporation of Delaware No Drawing.

wherein R1 to R4 are hydrogen or hydrocarbon, X is chlorine or bromine and R5 is hydrocarbon or halohydrocarbon. Neither is there any known convenient or economical method of preparing the corresponding aliphatic beta-haloamines which compounds have the general formula wherein R1 to R4 are hydrogen or hydrocarbon and X is chlorine or bromine.

It has now been discovered that the N-acyl derivatives of aliphatic beta-haloamines and corresponding aliphatic beta-haloamines can be obtained through hydrolysis of their imidohalides. However, these imidohalides are not obtainable by any published general method. [Von Braun, Ber. 38, 2340 (1905); Von Braun, Angew. Chemie, 47, 611 (1934).]

It is an object of this invention to provide a general method of preparing the imidohalides of N-acyl-beta-haloamines. Another object is to provide a convenient and economical method of preparing N-acyl-beta -haloamines and betahaloamines. A further object is to provide a new class of chemical compounds, the imidohalides of certain N-acyl-beta-haloamines. Other objects will appear hereinafter.

These objects are accomplished by the method of preparing the imidohalides of N-acyl-betahaloamines which comprises halogenating an ethvlenically unsaturated hydrocarbon containing Application March 21, 1949, Serial No. 82,697

from two to twelve carbon atoms with a halogen having an atomic number from 1'7 to 35 in contact with a nitrile which is present in an amount of at least one mole per mole of said ethylenically unsaturated hydrocarbon. The hydrolysis products are obtained by hydrolyzing the resulting imidohalide under neutral to acidic conditions to the corresponding N-acyl-beta-haloamine and beta-haloamine. It has now been discovered that N-acyl-beta-haloamines and beta-haloamines can be obtained readily and economically using as intermediates the imidohalides of aliphatic N-acyl-beta-haloamines, which are prepared by the new method described herein.

The imidohalides of N-acyl-beta-haloamines which are a new class ,of chemical compounds are characterized by (a) the alpha carbon of the acyl group having its remaining three valences attached solely to chlorine or bromine, alkyl groups of one to six carbon atoms, chloroor bromoalkyl groups of one to six carbon atoms, or cycloalkyl groups of five to six carbon atoms (b) the amine portion of the molecule containing besides the nitrogen and halogen atoms, only carbon and hydrogen, having from two to twelve carbon atoms, and having the nitrogen and halogen atoms both attached to adjacent aliphatic carbon atoms. These new products have the general formula wherein the Rs are hydrogen or hydrocarbon radicals which taken together have a total of one to ten carbon atoms, two of which Rs may form, together with the carbon atoms attached to the nitrogen and halogen, a fiveto six-membered carbon alicyclic ring; X represents a halogen of atomic number from 17 to 35, i. e., chlorine or bromine; and the Zs are halogens of atomic number from 1'? to 35, alkyl groups of one to six carbon atoms, chloroalkyl or bromoalkyl groups of one to six carbon atoms or cycloalkyl groups of five to six carbon atoms, and two of the Zs may be joined in a five to six carbon cycloalkyl ring.

The process of this invention is illustrated by the following set of equations, where the ethylenically unsaturated compound is shown in skeleton form:

imidochloride of- N-acyi-betachloroamine H 1 (acidic) JJ+NH| beta-chloroamine (as salt) In some cases, as will be apparent from the examples which follow, there is simultaneous substitution halogenation of the nitrile, affecting the carbon atom alpha to the nitrile carbon, or addi tion halogenation if an unsaturated nitrile is used, or both.

Some of the primary products of this process, 1. e.,the imidohalides, are stable only-in solution or at low or moderate temperatures. However, certain of these imidohalides are stable and can be isolated and stored. Examples of such stable imidohalides are those having the formula wherein the R's, Xs and Z's have the significance herein specified. These stable imidohalides are new and are included within the present invention.

The invention is illustrated in greater detail in the following examples, wherein parts are by weight.

Example I obtained by hydrolysis of the intermediate N- [(alpha-chloro-beta, beta, beta-trichloro)ethylidenel-beta-chloroet ylamine (the imidochloride of N- (beta-chloroet yl) trichloroacetamide) Anal: Calculated for C4HsONCl4: C, 21.3; H, 2.22; N, 6.22; CI, 63.0. Found: C, 21.63; H, 2.37; N, 6.34; Cl, 62.0.

An authentic sample of N-(beta-chloroethyl) trichloroacetamide was prepared by treating beta-chloroethylamine hydrochloride with trichloroacetyl chloride in dry dioxane in the presenee of pyridine. The reaction product after recrystallization from 50% aqueous ethanol contained 62.81% chloride and melted at Fl-785 C. A mixed melting point with the product prepared as described above showed no depression.

Example I! When the above reaction was repeated using a large excess of chlorine, a stable imidochloride was obtained as follows:

Into 82 parts (2 moles) of acetonitrile at 15 C. chlorine and ethylene were introduced simultaneously and with rapid stirring by means of two inlet tubes below the surface of the acetonitrile. Two and one-half hours were required for the introduction of 1.08 moles of ethylene. Chlorine was introduced simultaneously during this time and for 4.5 hours longer. After the ethylene addition was complete, the reaction temperature was allowed to rise to 30-35 C. until a total of 360 parts of chlorine had been added. The reaction mixture was purged with nitrogen until no hydrogen chloride was evolved, and distilled. A small amount of low boiling material was obtained which consisted of acetonitrile and 1,2-dichloroethane. The main fraction consisted of 122 parts of a colorless liquid boiling at 71-73 C. at 3 mm. pressure, a 15150. which was shown by analysis to be N-[(alpha-chloro-beta,- beta,beta trichloro) ethylidenel -beta-chloroethylamine,

the imidochloride of N-(beta-chloroethyDtrichloroacetamide.

Anal.: Calculated for omen: (:1, 72.87; N,

5.7a. Found: c1. 72.11; 1s. 5.83.

The imidochloride was hydrolyzed by heating 42 parts of it to reflux with parts of water, 80 parts of methanol and 18 parts of concentrated hydrochloric acid for 2 hours. On cooling, there was obtained a white crystalline solid (82% conversion) melting at 76-76.5 C. which after crystallization from benzene was found to be identical with the N- (beta-chloroethyl) trichloroacetamide of Example I.

Example 111 A solution of 15 parts (0.126 mole) of benzonitrile in '15 parts of chloroform was alternatively saturated with ethylene and chlorine at 10 C. until chlorine was no longer consumed. The mixture was then purged with nitrogen and the chloroform was evaporated. On cooling, 5.5 parts of a white solid was obtained and recrystallized from benzene. This was N-benzoyl-betachloroethylamine, ClCH2'CH2-NHCOC6H5, M. P. 104-1055 C., obtained through hydrolysis of the intermediate imidochloride by the small amount of moisture present in the reaction mixture.

Anal: Calculated for CeHmONCl: C], 19.35; N,

7.13. Found: Cl, 19.33; N, 7.33.

Example IV Chlorine and ethylene were introduced simultaneously into parts (2.35 moles) of acrylonitrile at 15 C. Complete absorption of both gases occurred and after 1% hours the reaction was stopped when 72 parts (1.02 moles) of chlorine and 18 parts (0.645 mole) of ethylene had been added. The mixture was purged with nitrogen and rectified. There was obtained 56 parts of a colorless liquid boiling at 94-95 C. at 4 mm. pressure, a 1.5200, which was shown by analysis to be N-[(alpha-chloro-beta,beta-dichlorogammachio'ro) propylidenel beta-chloroethylaQ mine, or the imidochloride o! N-(beta-chloroethyl) alpha,alpha,beta-trichloro-propionamlde. 'c1cn.-cm-N=c-cci,-cmc1 Anal.: Calculated for cannon: c1, sass; n, 5.47.

Found: Cl, 67.63;'N, 5.60.

Example V Anal.: Calculated for C'lHlJNCh: Cl, 39.01; N, 7.70.

Found: Cl, 38.71; N, 7.99.

When 13.5 parts or the imidochloride was poured into 100 parts of water, an immediate reaction occurred and so much heat was evolved that it was necessary to cool the mixture by direct addition of ice. From the cold mixture separated 7.5 parts of N-(beta-chloroethyDpivalamide, CICH2CH2NHCOC(CH3)3, a solid meltin at 162 C. 1

Anal.: Calculated for C-zHuONCl: Cl, 21.71; N,

8.57. Found: Cl, 21.13; N. 7.84.

Example VI A solution of 32 parts of chlorine in 135 parts of acetonitrile cooled in an ice bath was treated with a slow stream of isobutylene until the yellow color disappeared. The excess acetonitrile was removed, leaving 21 parts of colorless oil (n =1.5088) which did not crystallize and could not be purified by distillation. On hydrolysis of this material with dilute hydrochloric acid there was obtained a low melting colorless solid, from which an oily constituent was removed by rubbing on a clay plate. The solid melted at 53-54 C., and analyzed for an N-(chloroisobutyl)trichloroacetamide. Although the respective positions of the chloro and the amide groups were not definitely established, it is probable that the material was N-[(beta-chloro-alpha,alphadimethyl) ethyl] trichloroacetamide,

CH: om-c-im-c o-c ch HzCl obtained by hydrolysis of the intermediate N- Haipha chloro be a,beta,beta trichloro) ethylidene] (beta ch oro alpha,alpha dimethyl) -ethylamine.

Anal.: Calculated for CsHeONCh: C, 28.4; H, 3.56; N, 5.53; CI, 56.1. Found: C. 28.42; H, 3.51; N, 5.46; Cl. 55.6.

Example VII A slow stream of gaseous butadiene was bubbled while stirring through 50 parts 01. acetonitrile .cooled in an ice bath. while adding simultaneously a solution of 12.5 parts of chlorine in 50 parts of acetonitrile. The resulting colorless reaction mixture was evaporated to remove the excess.ac'etonitrile. There remained 13.4 parts of a yellowish oily product which was treated with concentrated hydrochloric acid at C. for

about 5 hours. The resulting solution was cooled, neutralized with alkali and extracted with ether. The ether solution after drying over anhydrous sodium sulfate was treated with dryhydrogen chloride, which gave a light brown oil consisting essentially of the hydrochloride or a monochloro monoaminobutene, as indicated by its chlorine content or 47.1% and its nitrogen content of 8.73%.

Example VIII Into a stirred mixture or 56 parts (0.5 mole) of octene-l and 41 parts (1 mole) of acetonitrile was bubbled 55 parts (0.77 mole) of chlorine at 10-15" C. The resulting clear solution was poured into a mixture of ice and water, and this mixture was treated With parts of concentrated hydrochloric acid and steam-distilled. The aqueous portion of the steam distillation residue was evaporated to dryness, leaving a solid amine hydrochloride which was recrystallized from a henzene-ethanol mixture. There was thus obtained 14 parts of crystalline material shown by analysis to be the hydrochloride of l-hydroxymethylheptylamine,

CBHiPCH-NHLHCI I HzOH Anal.: Calculated for CsHzoONCl: C1, 19.54; N,

7.72. Found: Cl, 20.31; N, 7.69.

Example IX A solution of 14 parts of chlorine in 50 parts of acetonitrile was added with stirring to a mixture of 41 parts of cyclohexene and 41 parts of acetonitrile at ordinary temperature. At the end of the slightly exothermic reaction, the excess acetonitrile and cyclohexene was removed by evaporation at 100 C., leaving an oily residue which did not crystallize and could not be purified by distillation. This material was hydrolyzed by treatment with 100 parts of nearly boiling water for a few minutes, giving a colorless crystalline solid which, after recrystallization from aqueous alcohol, melted at 127-130 C. Analysis indicated that this compound was N-(2-chlorocyclohexyl) -acetamide,

Hi0 CHCI H2O CHNHC O-GHI obtained by hydrolysis of the intermediate N- (alpha chloro ethylidene) 2 ch1orocyc lo hexylamine, the imidochloride of N-(2-chlorocyclohexyl) acetamide.

Anal.: Calculated for CaHuONCl: C, 54.7; H, 7.98; N, 7.98; CI, 20.25. Found: C, 54.64; H, 8.05; N, 7.37; Cl, 20.3.

A sample (15 parts) or N-(2-chlorocyclohexyl) acetamide was heated with 100 parts of 3 N bydrochloric acid for 24 hours and the solution was evaporated to dryness. The residual solid was v76 recrystallized from ethanol to give nearly the 2 chlorocyclohexyl formamide.

theoretical yield of 2-hydroxycyclohexylamine hydrochloride, M. P. 188-189 C.

Example X The presence 01 water, even in substantial amounts, is not detrimental to the process or chlorine-ting olefins in the presence or nitrile, as shown by the iollowing experiment.

Chlorine gas was passed into a vigorously stirred mixture of 41 parts (0.5 mole) of cyclohexene, 21 parts (0.5 mole) of acetonitrile and 50 parts of water. A white solid separated as chlorine was passed into the stirred solution. After the theoretical amount of chlorine had been added. the mixture was poured onto cracked ice and filtered. This gave 16 parts N-(2-chlorocyclohexyl) -acetamide, melting at 129-130 C. after crystallization from methanol.

Anal.: Calculated for CsHuONCl: Cl, 20.25;

N, 7.98. Found: 01, 20.10; N, 7.90.

The liquid by-product in this experiment consisted of 34 parts of dichlcrocyclohexane, B. P. 94 C. at 44 mm. pressure. n 1.4877.

Example XI A mixture of 31 parts (0.3 mole) of benzonitrile and 16.4 parts (0.2 mole) of cyclohexene was treated with 15 parts (0.21 mole) of chlorine gas at 5 C. The reaction mixture was poured into water and steam-distilled to remove the unreacted benzonitrile. The residue was cooled rapidly and the solid which separated was illtered. Recrystallization of this solid from benzene gave parts of N-(2-chlorocyclohexyl) benzamide,

HzC CHCl 1M. P. 165 C.

Anal: Calculated for CnHrsONCl: Cl, 14.94;

N, 5.89. Found: Cl, 15.01; N. 5.88.

Example XII A mixture of 82 parts (1 mole) of cyclohexene and 84 parts (3.1 moles) of hydrogen cyanide was treated at 10 C. with 85 parts (1.2 moles) of chlorine gas while maintaining rapid stirring The resulting mixturewas poured onto ice and the organic layer was separated and washed several times with water. The remaining organic liquid was refluxed with 200 parts of 3 N hydrochloric acid for 2 hours. The mixture was then treated with 20 parts of methanol, refluxed 2 hours longer and steam-distilled. The nonsteam volatile portion was filtered from about 2.5 parts of tarry material and evaporated to dryness. There was obtained 59 parts of Z-chlorocyclohexylamine hydrochloride, resulting from hydrolysis of the intermediate imidochloride of Recrystallization of the product from ethanol gave the pure 2-chlorocyclohexylamine hydrochloride, M. P. 213-2l4 C.

Anal; Calculated tor CcHnNCh: Cl,

N, 8.24. Found: Cl, 41.42; N, 8.03.

Example XIII treated with 58 parts (0.817 mole) of chlorine gas at 10-15 0., then purged with nitrogen. The reaction product was allowed to stand in contact with water for 60 hours, but no noticeable hydrolysis occurred. The mixture was then steam-distilled and the residualhon-steam volatile organic material was separated and taken up in benzene. The benzene solution was dried over calcium sulfate and evaporated.- leaving an oil which was treated with a little petroleum ether and cooled in a carbon dioxide-acetone bath. Crystallization took place, giving 11 parts of a while solid, melting at -l00 C. This was shown by analysis to be N-(2'-chlorocyclohexyl) 1, 1, 2-trichloropropionamide,

BIC CHCI H1O CH-NH-CO-C JlaCH1Cl UH: produced by hydrolysis of the intermediate imidochloride.

Anal: Calculated for CoHnONCh: Cl, 48.46;

N, 4.80. Found: Cl, 48.50; N, 4.50.

Example XIV H1O CHCI UH: produced by hydrolysis of the intermediate imidochloride.

AnaL: Calculated for CuHzoONCl: Cl, 16.30; N,

6.44. Found: Cl, 16.22; N, 6.41.

Example XV Chlorine gas (33 parts, 0.47 mole) was passed into a stirred solution 0! 41 parts (0.5 mole) or cyclohexene in 64 parts (0.75 mole) of acetone cyanohydrin at l0l5 C. in 45 minutes. The resulting clear solution was poured into an icewater mixture and allowed to stand for 15 hours. The mixture was cooled again and the white solid which had rlparated was filtered and recrystallized from ethanol, giving 11 parts of a crystalline product melting at l4'l-14'l.5 C. This was shown by analysis to be N-(2-chlorocyclohexyl) dimethyl-hydroxyacetamide,

HaC CHCl produced by hydrolysis of the intermediate imidochloride.

Anal.: Calculated for CioHwOzNCl: Cl, 16.16; N,

6.38. Found: Cl, 16.68; N, 6.47.

9 Example XVI Chlorine gas (27 parts, 0.38 mole) was bubbled into a stirred solution oi 2'7 parts (0.2 mole) of dipentene and 125 parts (4.6 moles) of liquid hydrogen cyanide at 5 C. in 1 hour. The reaction mixture was poured into an ice-water mixture and the organic layer was separated and washed with water several times. The oil was then heated with 100 parts of 6 N hydrochloric acid at 100 C. and the resulting solution was evaporated to dryness. Final drying was achieved by adding benzene and distilling out a binary of water and benzene. The remaining tan-colored solid was purified by dissolving it in methanol, filtering the solution and reprecipitating the product by pouring the solution into a large volume of anhydrous ether. The solid reaction product had a melting range of 150-172 C. and it consisted chiefly of the hydrochloride ot a monochloro monoamino addition product of dipentene.

Anal: Calculated for CroHuNClz: 01, 31.70; N, 6.25; ionic chlorine, 15.85. Found: Cl, 30.05; N, 7.34; ionic chlorine, 17.81.

Example XVII Chlorine gas (118 parts, 1.66 mole) was bubbled into a stirred mixture of 18.7 parts (1.8 moles) of styrene and 185 parts (4.5 moles) of acetonitrile at 5-10" 0. over a period of 2 hours. The reaction mixture was poured onto ice and allowed to stand hears. Some solid material separated during this time and more was recovered by successivelv cooling the mixture in an ice bath and the organic phase of it in a carbon dioxide-acetone bath. A total of 93 parts of air dried product was obtained, which after recrystallivation from ethyl acetate melted at 103- 104 C. This was shown bv analysis to be N-(2- chloro-1-phenyl) ethyl acetamide,

cmcl (hm-c6 Nncocm produced by hydrolysis oi the intermediate imidochloride, N-(alpha-chloroethylidene) -1-phenyl-2-chloroethylamine.

, AnaL: Calculated for Cml-ImONCl: Cl, 17.97; N,

7.09. Found: C1, 18.11; N, 6.59.

M. P. 132-135 C. This compound appears to decompose at the initial melting point, resolidify and subsequently remelt at 147-149 C. These observations confirm those published by Gabriel and Colman, Ber. 47, 1866.

Anal; Calculated for CsHrzQNCl: Cl, 20.46; N,

8.07. Found: Cl, 20.22; N, 7.95.

10 Ewample xvm amine hydrochloride. The latter product was recrystallized from an ethanol-ethyl acetate mixture to give a white solid, M. P. 1'74-178 C., which was shown by analysis to be alpha-phenylbeta-chloroethylamine hydrochloride,

ClCHr-CH-NHz-HCI oHu produced by hydrolysis of the intermediate imidochloride of N-(alpha-phenyl-beta-chloro) ethyl iormamide.

AnaL: Calculated for CsHuNCh: Cl, 36.97; N, 7.30 ionic chlorine, 18.49. Found: Cl, 36.51; N, 7.22; ionic chlorine, 18.16.

Example XIX A solution of 11.8 parts of 2,5-dihydrothlophene-Ll-dioxide (the addition product of sulfur dioxide to 1,3-butadiene, having the structure CH=CH (EH: CH1) in 41 parts of acetonitrile was treated'with chlorine gas, bubbled therethrough in a slow stream at about 20 C., until the solution became light yellow in color. The reaction mixture was cooled in an ice bath and the colorless precipitate which separated was filtered off. There was thus obtained 10.2 parts of product melting at 129-130" v C., which upon recrystallization from methanol or benzene gave colorless crystals melting at 136-140! 0. Additional product can be obtained by concentration of the acetonitrile filtrate.

The reaction product was shown by analysis to have the composition CcHcOzNSCls, which indieated that it was the imidochloride, N-[(alpha chloro beta,beta,beta trichloro)ethylidene]-3- chloro -4- aminotetrahydrothiophene-1,1-dioxide, which may alternatively be called 3-chloro-4- (alpha-chloro-beta,beta,beta-trichloro) acetaldiminotetrahydrothiophene-1,1-dioxide, having the formula ClCHCH-N=CCCh Anal.: Calculated for CsHcOzNSCls: N, 4.20; S, 9.60; Cl, 53.2. Found: N, 4.30; S, 9.44; Cl, 52.5.

Hydrolysis of the above-described product by treatment with concentrated hydrochloric acid at C. for about 5 hours, followed by cooling and filtering, gave a colorless solid which after recrys tallization from benzene melted at 202-205 C. Analysis showed that the hydrolysis product was 3 chloro-4-(trichloroacetamido) tetrahydrothiophene-1,1-dioxide,

Anal.: Calculated for CsHIOsNSChZ N, 4.44; S, 10.16; C1, 45.1. Found: N, 4.29; S, 9.94; Cl, 44.9.

11 Example XX Chlorine was passed into 50 parts of acetonitrile cooled in an ice bath until 15.6 parts had dissolved- To this solution was then added a solution of 8.8 parts of 2,5-dihydrothiophene-1,1-dioxide in 18 parts of acetonitrile, whereupon the yellow color of the chlorine solution disappeared in a few minutes. The excess acetonitrile was removed by evaporation and there was recovered 17.6 parts of a colorless crystalline solid. This product was recrystallized from hot methanol and this treatment apparently replaced the labile chlorine atom on the carbon in alpha position to the nitrogen by a methoxy group, since the material analyzed for N-[(alpha-methoxy-beta,beta,di chloro) ethylidene] -3-chloro-4-aminotetrahydrothiophene-Ll-dioxide, which may also be called 3-chloro-4- (alpha-methoxy beta,beta,dichloro) acetaldiminotetrahydrothiophene 1,1 dioxide, M. P. 158-160 C. This compound has the formula Anal; Calculated for C'lHmOaNSCla: N, 4.75; S, 10.87; Cl, 36.2. Found: N, 4.74; S, 11.8; C1, 35.8.

Hydrolysis of this product by treatment with nearly boiling water for a few minutes gave a colorless solid melting at 170-1'73 C., which analysis showed to be 3-chloro-4-(dichloroacetamide) tetrahydrothiophene-1,1-dioxide,

Ci-CHCH-NH-C-CHCh I Anal.: Calculated for CoHaOaNSCla: C, 25.7; H, 2.85; N, 4.99; S, 11.4; C1, 38.0. Found: C, 25.51; H, 2.85; N, 4.90; S, 11.3; CI, 37.5.

When the hydrolysis was carried out with a mixture of 3 parts of concentrated hydrochloric acid and one part of water at 100 C. for 2 hours, the product was a colorless solid melting at 218- 220" C. which analysis showed to be the hydrochloride of 3 chloro 4 aminotetrahydrothiophene-Ll-dioxide,

Anal.: Calculated for C4H90-NSClz: N, 680; S, 15.54; Cl. 34.45; neutralization equivalent, 206. Found: N, 6.74; S, 15.46; Cl, 34.10; neutralization equivalent. 200.

Example XXI Bromine 115 parts. 0.72 mole) was a ded dronwise to a stirred solut on of 82 parts .0 mole) of cyclohexene in 164 parts (4 0 moles) of acetonitrile at -5 C. over a period of 75 minutes. The reaction mixture was immediately poured onto cracked ice and allowed to stand for 24 hours at room temperature. The resulting mixture was cooled again and filtered. The solid (41.5 parts) was crude N-acetyl-2-bromocyclohexylamine obtained by hydrolysis of the intermediate N-(alpha-bromoethylidene) -2-bromocyclohexylamine, the imidobromide of N-(2-bromocyclohexyl)-acetamide. After recrystallization from ethyl acetate, N-acetyl-2-bromocyclohexylamine was obtained as a white solid melting at 109-110 C.

Anal: Calculated for CsH14ONBr: Br, 36.34;,

6.36. Found: Br, 36.54; N, 6.28.

This invention includes as new products the imidochlorides and imidobromides of the general formula wherein the R's, X's and Z's have the significance herein stated. These imidohalides are heatstable, distillable liquids which, in addition to their use as intermediates in the preparation of N-acyl-beta-haloamines, are useful per se as pest killers, insecticides, bactericides, and the like. The preferred compounds, because most accessible, are the imidochlorides, in particular those in which at least two of the radicals R1, Ra, R3 and R4 are hydrogen and the others are aliphatically saturated hydrocarbon radicals each containing from one to six carbon atoms but having a total of not more than ten carbon atoms, or are methylene radicals Joined together with the carbon atoms attached to nitrogen and chlorine to form a 5 to 6 member alicyclic ring.

Z1 mc-cHr-N=c- ';-za

l l I wherein the Z's are chlorine, allcyl of one to six carbon atoms or chloroalkyl of one to six car-- bon atoms.

In addition to the several imidohalides described in the examples, there may be mentioned, as other members of this class, the imidochlorides of N-(2-chloroethyl) -dimethylchloroacetamide, N (2 chloropropyl)methyldibromoacetamide, N (2 chlorododecyl) trichloroacetamide, N-(2-chlorocyclohexyl)trimethyl acetamide, N- (2-chloroethyl) -tri (chloromethyl) acetamide, N-(Z-chloro-l-phenyl) ethyl trichloroacetamide, N (2 chlorobutyl) cyclohexyldibromoacetamide, N- (2- -chloroethyl) hexyldimethylacetamide, N (2 chloroethyl) l-methylcyclohexanecarbonamide; N- (2-chloro-2,2-dimethyl- 1,1 dimethyl) ethylltrichloroacetamide, N (2- bromobutyl)-cyclopentyldimethylacetamide, N- [(2 chloro-l-naphthyl) ethyllchlorohexyldimethylacetamide, N-(Z-chloroethyl) tri (cyclohexyl) acetamide; the imidobromides of N-(2- bromoethyl) -tri(bromomethyl) acetamide, N-(2- bromopropyl) tributyiacetamide, N (2 bromocyclopentyl)tribromoacetamide, and the like.

In the process of this invention there may be used any ethylenically unsaturated hydrocarbon having from 2 to 12 carbon atoms. In addition to the unsaturates used in the examples, other suitable unsaturates include propylene, butene-I, the amylenes, hexene-l, dodecene-l,

ammo

with unsaturates which. in addition to carbon Any nitrile, including hydrogen cyanide (formonitrile), is suitable for use in the process of this invention, including, in addition to the nitriles used in the examples, propionitrile, butyronitrile, capronitrile, heptanonitrile, dodecanonitrile, stearonitrile, olenitrile, cyclohexane carbonitrile, naphthonitriie, chloroacetonitrile, trichloroacetonitrile, carbethoxyacetonitrile, succinonitrile. adiponitrile and the like. The preferred nitriles are the mononitriles containing only carbon and hydrogen in addition to. the nitrile nitrogen, in particular those containing from two to'twelve carbon atoms. The most useful mononitriles are the alkanenitriles of two to twelve carbon atoms.

The halogenation of ethylenic compounds in the presence of a nitrile can be carried out under a fairly wide variety of conditions. To obtain satisfactory yields it is desirable to use at least one mole of nitrile per mole of ethylenic compound, and there may be used as much as or moles or even more although it is-uneconomical to use such an excess of nitrile. The ethylenic compound need not be completely dissolved in the nitrile, although this is preferable. If desired, an inert auxiliary solvent such as carbon tetrachloride or chloroform may be used. The halogen (bromine or chlorine) can be added to the mixture of nitrile and ethylenic compound, or the latter can be treated with a solution of halogen in the nitrile. If an excess of halogen is used, substitution reactions may take place, involving in particular the imidohalide portion of the molecule. Such reactions can in general be avoided, if desired, by operating with a slight excess of unsaturated compound.

The halogenation reaction proceeds in general very well in the cold. e. g., at temperatures between -50 and +20 C., but higher temperatures, e. g., up to 100 C. or more may be used. At high temperatures substitution reactions may tend to be excessive. The course of the halogenation can easily be followed either through tests for residual free halogen or by periodic examination of a sample of the reaction product. The best results are obtained when the molaramount of halogen used is approximately equivalent to or higher than that of the unsaturate, e. g., between 0.7 an 3.0 moles of halogen per mole of unsatur but there may be used if desired as low as 0. 5 mole of halogen per mole of unsaturate and as high as 5 moles or even more. The halogen preferably used is, of course, chlorine.

The primary reaction product, i. e., the imidohalide, may be isolated by any convenient means,

such as by crystallization from the reaction mixi the corresponding amides or amines, depending i4. on the stability of thestarting material and on the severity or the hydrolysis conditions. Neutral or acidic hydrolysis conditions should be used to obtain the amides and beta-haloamines since they are unstable under alkaline conditions. Hydrolysis is suitably carried out with water alone, e. g., at temperatures between 0 C. and 100 0., or with dilute or concentrated acids such as hydrochloric or sulfuric acid, if desired, at

elevated temperatures up to 100 C. or higher (in closed vessels). The hydrolysis products may be purified by recrystallization from suitable solvents. or from water in the case of .the'betahaloamine hydrohalides.

The invention provides an economical and rapid method of-arriving, through the intermediate imidohalides, at halogenated, amides and amines which are useful as insecticides, plasticiaers, etc., and as intermediates for numerous chemical syntheses.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof it is to be understood that this invention is not limited to the specific embodiments thereof except as defined in the appended claims. I claim:

1. An imidochloride of an N-acyl-beta-chloroamine having the following general formula wherein R1, Ra, R: and R4 are members oi the group consisting of hydrogen, phenyl, alkyl radicals of from 1 to 6 carbon atoms, and methylene radicals joined together with the carbon atoms attached to nitrogen and chlorine to form a 5 to 6 membered alicyclic ring, at least two of said members R1. R2, R: and R4 being hydrogen, the total number of carbon atoms in said members R1, Ra. R; and R4 not exceeding ten, and Z1, Z2 and Z: are members of the group consisting of chlorine, alkyl of 1 to 6 carbon atoms and chloromethyl.

2. N [(alpha chloro beta,beta,beta trichloro) -ethylidenel -beta-chloroethylamine.

3. A process for the preparation of an imidohalide of an N-acyl-beta-haloamine which comprises halogenating at a temperature of -'50 to 100 C. ethylenically unsaturated hydrocarbon containing from 2 to 12 carbon atoms with a halogen having an atomic number of 17 to 35 in contact with a nitrile which is present in an amount of at least one mole per mole oi. said ethylenically unsaturated compound.

4. A process which comprises halogenating at a temperature of -50 to 100 C. an ethylenically unsaturated hydrocarbon containing from 2 to 12 carbon atoms with a halogen having an atomic number of 17 to 35 in contact with a nitrile which is present in an amount of at least one mole per mole of said ethylenically unsaturated compound and hydroLvzing under neutral to acidic conditions the resulting imidohalide.

5. A process for the preparation of an imidochloride of an N-acyl-beta-chloroamine which comprises halogenating at a temperature of 50 to 100 C. an ethylenically unsaturated hydrocarbon containing from 2 to 12 carbon atoms with chlorine in contact with a nitrile containing only carbon and hydrogen in addition to the nitrile nitrogen, said nitrile being present in an i amount of at least one mole per mole of said ethylenicaliy unsaturated compound.

8. A process which comprises halogenating at a temperature of 50 to 100 C. an ethylenically unsaturated hydrocarbon containing from 2 to 12 carbon atoms with chlorine in contact with a nitrile containing only carbon and hydrogen in addition to the nitrile nitrogen, said nitrile being present in an amount of at least one mole per mole of said ethylenically unsaturated compound and hydrolyzing under neutral to acidic conditions the resulting imidochloride.

7. A process for the preparation of an imidochloride of an N-acyl-beta-chloroamine which comprises halogenatlng at a temperature of 50 to 100 C. an ethylenlcally unsaturated hydrocarbon containing Irom 2 to 12 carbon atoms with chlorine in contact with a mononitrile containing only carbon and hydrogen in addition to the nitrile nitrogen, said nitrile being present 16 in an amoimt or at least one mole per mole of said ethylenically unsaturated compound,

8. A process for the preparation or an imidochloride of an N-acyl-beta-chloroamine which comprises halogenating at a temperature of to C. an ethylenically unsaturated hydrocarbon containing from 2 to 12 carbon atoms with chlorine in contact with acetonitrile which is present in an amount of at least one mole per mole of said ethylenicaliy unsaturated compound.

9. A process for the preparation of an ixnidochloride of an N-acyl-beta-chloroamine which comprises halogenating at a, temperature of 50 to 100 C. ethylene with chlorine in contact with acefonitrile which is present in an amount of at least one mole per mole of said ethylene.

PAUL L.- BARRICK.

No references cited. 

1. AN IMIDOCHLORIDE OF AN N-ACYL-BETA-CHLOROAMINE HAVING THE FOLLOWING GENERAL FORMULA
 3. A PROCESS FOR THE PREPARATION OF AN IMIDOHALIDE OF AN N-ACYL-BETA-HALOMINE WHICH COMPRISES HALOGENATING AT A TEMPERATURE OF -50* TO 100* C. ETHYLENICALLY UNSATURATED HYDROCARBON CONTAINING FROM 2 TO 12 CARBON ATOMS WITH A HALOGEN HAVING AN ATOMIC NUMBER OF 17 TO 35 IN CONTACT WITH A NITRILE WHICH IS PRESENT IN AN AMOUNT OF AT LEAST ONE MOLE PER MOLE OF SAID ETHYLENICALLY UNSATURATED COMPOUND. 